CN102034985B - Oxygen electrode of lithium air battery as well as preparation method and application thereof - Google Patents
Oxygen electrode of lithium air battery as well as preparation method and application thereof Download PDFInfo
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- CN102034985B CN102034985B CN2010105485674A CN201010548567A CN102034985B CN 102034985 B CN102034985 B CN 102034985B CN 2010105485674 A CN2010105485674 A CN 2010105485674A CN 201010548567 A CN201010548567 A CN 201010548567A CN 102034985 B CN102034985 B CN 102034985B
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Abstract
The invention relates to an oxygen electrode of a lithium air battery. Active materials of the oxygen electrode are loaded on a porous TiN nano tube; and the active materials are deposited or loaded in a conducting network consisting of a porous TiN nano structure by an electrodeposition, chemical deposition or high-temperature nitridation method. By utilizing the oxygen electrode, the contents of noble metal and an adhesive in the oxygen electrode material can be omitted or reduced, therefore, the cost of the lithium air battery is greatly reduced; and in the oxygen electrode is simple in structure, easy for assembly and convenient in use.
Description
Technical field
The invention belongs to the lithium-air battery technical field, be specifically related to a kind of lithium-air battery oxygen electrode.
The invention still further relates to the preparation method of above-mentioned lithium-air battery oxygen electrode.
Background technology
Along with the development of society, energy problem and environmental problem are increasingly sharpened, energy-saving and emission-reduction and tap a new source of energy and efficiently Energy device be the important topic of society.Recent two decades comes, and has dominated the development of heavy-duty battery take lithium metal as the battery on basis, and this is because lithium metal has minimum density, the highest voltage, best electronic conductance and the highest electrochemical equivalent.Actively developed in global range and improved the energy density of lithium battery and the research of electrode material stability.LiCoO
2With material with carbon element as the successful commercialization of the positive and negative pole material of lithium ion.But along with skyrocketing of fossil class A fuel A price, replace the petroleum-type product by efficient power supply, thereby for motor vehicles provide the power support, become an urgent demand of modern social development.Seek specific energy higher, more cheap positive electrode is the developing direction of lithium battery always, but in lithium battery, positive electrode has limited to the energy storage capacity of lithium battery, such as the electrochemistry capacitance of lithium metal is 3860mAh/g, but the electrochemistry capacitance of most of positive electrode only has 200mAh/g, in addition, lithium ion is lower at the diffusion coefficient of metal positive-pole material, has also limited the energy output of lithium battery.
On the other hand, lithium-air battery has good chemical property, as a kind of brand-new metal-air cell, does not need to be stored in battery as the oxygen (air) of positive pole.Aerial oxygen can become negative oxygen ion or cross negative oxygen ion and then generate metal oxide or peroxide by electrochemical reaction by catalyst.Its operation principle is as follows:
In organic system:
4Li+O
2→2Li
2O (1)
2Li+O
2→Li
2O
2 (2)
In inorganic solution:
Calculate by reaction (1), the open circuit voltage of battery is 2.91 volts, and theoretical energy density is 5200Wh/kg, in actual applications, oxygen is provided by external environment, after therefore removing the quality of oxygen, energy density reaches 11140Wh/kg, exceeds an existing battery system 1-2 order of magnitude.Huge energy density has determined that lithium-air battery will be widely used in aviation and mobile energy field.But the oxygen electrode of positive electrode current is generally noble metal catalyst (as Pt), and the cost of the empty battery of lithium is increased, and restricts the developing steps of its industrialization.If can successfully adopt new catalyst to replace or reduce the use of noble metal, with greatly reducing the cost of lithium-air battery, great progradation be played in the development of lithium-air battery.
The research of lithium-air battery is at the early-stage, the relevant report seldom, and K.M.Abraham reports the article of lithium-air battery first, has introduced take gelatin polymer as electrolytical lithium-air battery.J.Read forms direction at lithium-air battery discharge mechanism, electrode material and electrolyte and has done a large amount of work.Because peroxide and lithia all are not dissolved in organic electrolyte, therefore, discharging product can only be to precipitate on oxygen electrode, in the situation that anode is excessive, the termination of discharge is because discharging product is stopped up due to the air electrode duct.The people such as Imanishi have avoided Li by the stable diaphragm material of preparation water environment
2O, Li
2O
2Accumulation, reduce the polarization charge and discharge.P.G.Bruce makes major contribution in the research of lithium-air battery charging mechanism, this studies show that battery has the property of charging and discharging when discharging product is lithium peroxide.
The patent of lithium-air battery is fewer, K.M.Abraham once reported based on the PAN-PVDF system and got lithium-oxygen battery system (patent No. US5561004), and other patent includes only a few things aspect ionic liquid (US4804448) and positive electrode (US71477967) such as Eltron company.Yu Aishui etc. have reported high ratio energy chargeable full-solid lithium air battery (CN101267057A).
The oxygen electrode of lithium-air battery is mainly concentrated at present is as catalyst material with precious metals pt, relevant report document is less, wherein N.Imanishi etc. reported a kind of with the Pt net as catalyst, the oxygen electrode end is the lithium-air battery of aqueous electrolyte, the Open Circuit Potential that is lithium-air battery is brought up to 3.8V, has reduced simultaneously the polarization phenomena between charge and discharge platform.Summer forever Yao group reported a kind ofly with the lithium-air battery of mesoporous carbon as catalyst, its discharge capacity is higher than with the lithium-air battery of carbon black as catalyst.The week person of outstanding talent is gloomy waits the people once to report with Mn
3O
4As the lithium-air battery of catalyst, its specific capacity can reach 50,000mAhg
-1Up to the present, not yet have based on the conductive network of the TiN nanostructure report as conductive carrier load electro catalytic activity material.
Summary of the invention
The object of the present invention is to provide a kind of tool lithium-air battery oxygen electrode.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned lithium-air battery oxygen electrode.
For achieving the above object, lithium-air battery oxygen electrode provided by the invention has the active material of oxygen electrode in the load of TiN nano-tube array, and nested active material is for open coaxial sleeve structure or fill club shaped structure completely; Active material is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; The content of noble metal (platinum, gold) is less than 5% of oxygen electrode gross mass.
The method of the above-mentioned lithium-air battery oxygen electrode of preparation provided by the invention, key step is:
A) with the Ti sheet at NH
4Carry out the anode electrochemical corrosion in F, wherein Ti is as anode, and the Pt sheet is as negative pole;
B) product that obtains of step 1 is in NH
3In atmosphere, 800-1000 ℃ of reduction, obtain the TiN nano-tube array;
C) deposit in the TiN nano-tube array by the active material of electrochemical deposition with oxygen electrode.
Lithium-air battery oxygen electrode provided by the invention, the active material of oxygen electrode can also be arranged based on the load of TiN mesoporous microsphere, the TiN mesoporous microsphere is to be become to possess the mesoporous micro-sphere structure of gradient by nano level TiN particle packing, coats in its surface and space and the deposition active material; Active material is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; The content of noble metal (platinum, gold) is less than 5% of oxygen electrode gross mass.
Described lithium-air battery oxygen electrode, wherein, the diameter＞50nm of TiN mesoporous microsphere, the specific area＞50m of TiN mesoporous microsphere
2g
-1
The method of the above-mentioned lithium-air battery oxygen electrode of preparation provided by the invention, key step is:
A) butyl titanate is mixed with ethylene glycol, add in acetone and stir, collect the deposit that generates;
B) grind deposit, with 80-100 ℃ of backflow of redistilled water, collecting precipitation material;
C) with deposit and amine cyanogen respectively at disperseing in distilled water, two groups of solution are mixed continue ultrasonic dispersions;
D) with active material ultrasonic dispersion in the mixed solution of step 3 of oxygen electrode, volatile dry obtains blocks of solid;
E) blocks of solid is placed in NH
3800-1000 ℃ of reduction in atmosphere;
F) the product binding agent with step 5 mixes, and is expressed to carbon online.
Described preparation method, wherein active material is: Pt nanoparticle, gold nano grain, α-MnO
2, β-MnO
2, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle, ternary metal nitride; The content of noble metal (platinum, gold) is less than 5% of oxygen electrode gross mass.
Lithium-air battery oxygen electrode of the present invention has good conducting matrix grain, simultaneously load the active material of catalytic oxygen, when guaranteeing good catalytic activity, removed or reduced the consumption of noble metal platinum in the oxygen electrode or gold and binder from.
Description of drawings
Fig. 1 a and Fig. 1 b are the stereoscan photographs of TiN nano-tube array; Wherein, Fig. 1 a is the sectional view of TiN nano-tube array, and Fig. 1 b is the plane graph of nano-tube array.
Fig. 2 a and Fig. 2 b are the stereoscan photographs of TiN mesoporous microsphere; Fig. 2 a stereoscan photograph that is the TiN Mesoporous Spheres under low multiplication factor wherein, Fig. 2 b are than the stereoscan photograph under high-amplification-factor.
Fig. 3 is the cyclic voltammetry curve of Pt/TiN nanometer pipe array electrode catalytic reduction oxygen.
Embodiment
Lithium-air battery oxygen electrode of the present invention, this electrode provides conductive network by the nanostructure of TiN, by chemistry, electrochemical deposition load oxygen activity material, is a kind of new and effective lithium air oxygen composite electrode system.
The present invention deposits the active material that the oxygen electricity is urged the utmost point on the conductive network of TiN nanostructure, play the efficient catalytic oxygen reduction, and the effect of reduction battery polarization current potential, Novel lithium air cell based on this oxygen electrode structure, Open Circuit Potential can reach＞3.4V, polarization potential between charge and discharge platform is poor is＜0.9V, and its specific capacity can reach＞800Ah g
-1
Lithium-air battery oxygen electrode of the present invention can build based on the TiN nano-tube array, and as shown in Figure 1, the thickness of TiN nano-tube array can reach 20 μ m, and the internal diameter of pipe is 50-100nm, and the thickness of tube wall is about 10nm.Its active material can be Pt nanoparticle, gold nano grain, MoN nano particle; α-MnO
2, β-MnO
2, γ-MnO
2In nano particle, ternary metal nitride, one or more are compound.Wherein the active material structure is the club shaped structure of opening the coaxial sleeve structure or filling fully.
Lithium-air battery oxygen electrode of the present invention can also build based on the TiN Mesoporous Spheres of specific area, as shown in Figure 2, the TiN mesoporous microsphere is to have the particle packing about 10nm to form, and possesses the mesoporous micro-sphere structure of gradient, its diameter range can regulate and control, between＞50nm.Its specific area is at＞50m
2g
-1Between.In its surface and space, the active material that coats and deposit can be Pt nano particle, gold nano grain, MoN nano particle, α-MnO
2, β-MnO
2, γ-MnO
2In nano particle, ternary metal nitride one or more, bullion content is less than 5% of oxygen reduction electrode quality.
The below further sets forth the present invention with embodiment, but the present invention is not so limited.
Embodiment 1
The Ti sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ti is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.The TiO that obtains
2Nano-tube array is at 800 ℃, NH
3High temperature reduction 1h in atmosphere obtains the TiN nano-tube array.By electrochemical deposition with the nanoparticle deposition of Pt in the TiN nano-tube array, electrolyte is 0.25mM H
2PtCl
6Be dissolved in 0.1M HCl, carry out electro-deposition by cyclic voltammetry.Potential region is-0.6～0.1V, and sweep speed is 20mVs
-1, deposit 10 circulations, namely obtain the coaxial sleeve structure of Pt/TiN.This combination electrode is the square pole piece of 1cm * 1cm, thickness is 100 μ m, and wherein the TiN nano-tube array thickness of supporting Pt nano particle is 20 μ m, and the internal diameter of sleeve structure is 30-40nm, Pt nano particle layer thickness is 10-15nm, and the pipe thickness of TiN nanotube is 10-15nm.This combination electrode can be to O
2Carry out efficient catalysis (as shown in Figure 3), and can directly as the oxygen electrode of lithium-air battery, need not additionally to add collector binding agent and conductive agent.Specific capacity based on the lithium-air battery of this oxygen reduction electrode can reach 1500mAh g
-1Open Circuit Potential can reach 3.6V.Potential difference between charge and discharge platform is 0.6V.
Embodiment 2
Diameter 200nm TiO
2The preparation of Mesoporous Spheres: the 2mL butyl titanate is mixed with 50mL ethylene glycol, stir 8h, add afterwards in the mixed solution of 170mL acetone and 2.7mL water, stirred 1 hour, the deposit that centrifugal collection generates is used absolute ethyl alcohol eccentric cleaning five times.Collecting precipitation, 80 ℃ of dried overnight are ground and are obtained white powder, and with this deposit 80 ℃ of backflow 3h of redistilled water, centrifugal collecting precipitate matter is used distilled water eccentric cleaning five times.Collecting precipitation, 80 ℃ of dried overnight, grinding obtains white powder and is TiO
2Mesoporous Spheres.
With 119mg TiO
2Mesoporous Spheres, 221mg amine cyanogen (Ti: N=1: 7) respectively at ultrasonic dispersion 5min in 2mL distilled water, two groups of solution are mixed continue ultrasonic dispersion 20min, the 10mg ammonium molybdate is dissolved in this mixed solution, ultrasonic dispersion 20min stirs volatile dry with 80 ℃ of the turbid liquid of ultrasonic scattered mixing.The blocks of solid that obtains is placed in tube furnace, at NH
3800 ℃ of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 ℃ of min
-1Obtain black powder and be the MoN/TiN Mesoporous Spheres.By this powder is mixed with 10% binding agent PVDF, utilize the 15Mpa pressure extrusion online to carbon, namely obtain MoN/TiN NEW TYPE OF COMPOSITE oxygen electrode.Lithium-air battery specific capacity based on this oxygen reduction electrode can reach 800mAh g
-1Open Circuit Potential can reach 3.5V.Potential difference between charge and discharge platform is 0.8V.
Embodiment 3
The Ti sheet is cleaned up with ethanol, is 0.5% NH at mass fraction
4In the ethylene glycol solution of F, carry out the anode electrochemical corrosion, wherein Ti is as anode, and the Pt sheet is as negative pole.The anodic attack current potential is 60V, and etching time is 8h.With the TiO that obtains
2Nano-tube array is placed in the ammonium molybdate solution 1h of 1mM, afterwards the pole piece that takes out carefully rinsed with clear water, and 280 ℃ of oven dry 3h, will obtain load has MoO
3TiO
2Nano-tube array is placed in tube furnace, at NH
3800 ℃ of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 ℃ of min
-1Can obtain the combination electrode of MoN/TiN nano-tube array.
Embodiment 4
Diameter 200nm TiO
2The preparation of Mesoporous Spheres: the 2mL butyl titanate is mixed with 50mL ethylene glycol, stir 8h, add afterwards in the mixed solution of 170mL acetone and 2.7mL water, stirred 1 hour, the deposit that centrifugal collection generates is used absolute ethyl alcohol eccentric cleaning five times.Collecting precipitation, 80 ℃ of dried overnight are ground and are obtained white powder, and with this deposit 80 ℃ of backflow 3h of redistilled water, centrifugal collecting precipitate matter is used distilled water eccentric cleaning five times.Collecting precipitation, 80 ℃ of dried overnight, grinding obtains white powder and is TiO
2Mesoporous Spheres.
With 119mg TiO
2Mesoporous Spheres, 221mg amine cyanogen (Ti: N=1: 7) respectively at ultrasonic dispersion 5min in 2mL distilled water, two groups of solution are mixed continue ultrasonic dispersion 20min, 80 ℃ of the turbid liquid of ultrasonic scattered mixing are stirred volatile dry.The blocks of solid that obtains is placed in tube furnace, at NH
3800 ℃ of high temperature reductions in atmosphere, in temperature-rise period, programming rate is 5 ℃ of min
-1Obtain black powder and be the TiN Mesoporous Spheres.By this powder is mixed with 10% binding agent PVDF, utilize the 15Mpa pressure extrusion online to carbon, carry out the electro-deposition of Pt on this electrode, electrolyte is 0.25mMH
2PtCl
6Be dissolved in 0.1M HCl, carry out electro-deposition by cyclic voltammetry.Potential region-0.6～0.1V, sweep speed is 20mVs
-1, deposit 10 circulations, namely obtain the combination electrode of Pt/TiN Mesoporous Spheres.Lithium-air battery specific capacity based on this oxygen reduction electrode can reach 1200mAh g
-1Open Circuit Potential can reach 3.8V.Potential difference between charge and discharge platform is 0.7V.
Claims (5)
1. lithium-air battery oxygen electrode has the active material of oxygen electrode in the load of TiN nano-tube array, nested active material is for open coaxial sleeve structure or fill club shaped structure completely;
Active material is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle; Wherein the content of noble metal is less than 5% of oxygen electrode gross mass.
2. lithium-air battery oxygen electrode has the active material of oxygen electrode in the load of TiN mesoporous microsphere, mix with adhesive, is expressed to carbon online;
The TiN mesoporous microsphere is to be become to possess the mesoporous micro-sphere structure of gradient by nano level TiN particle packing, coats in its surface and space and the deposition active material;
Active material is: Pt nanoparticle, gold nano grain, α-MnO
2Nano particle, β-MnO
2Nano particle, γ-MnO
2One or more in nano particle, MoN nano particle, MnN nano particle; Wherein the content of noble metal is less than 5% of oxygen electrode gross mass.
3. lithium-air battery oxygen electrode according to claim 2, wherein, the diameter＞50nm of TiN mesoporous microsphere, the specific area＞50m of TiN mesoporous microsphere
2g
-1
4. method for preparing the described lithium-air battery oxygen electrode of claim 1, key step is:
A) with the Ti sheet at NH
4Carry out the anode electrochemical corrosion in F, wherein Ti is as anode, and the Pt sheet is as negative pole;
B) product that obtains of steps A is in NH
3In atmosphere, 800-1000 ℃ of reduction, obtain the TiN nano-tube array;
C) deposit in the TiN nano-tube array by the active material of electrochemical deposition with oxygen electrode.
5. method for preparing the described lithium-air battery oxygen electrode of claim 2, key step is:
A) butyl titanate is mixed with ethylene glycol, add in acetone and stir, collect the deposit that generates;
B) grind deposit, with 80-100 ℃ of backflow of redistilled water, collecting precipitation material;
C) with deposit and amine cyanogen respectively at ultrasonic dispersion in distilled water, two groups of solution are mixed continue ultrasonic dispersions;
D) with active material ultrasonic dispersion in the mixed solution of step C of oxygen electrode, volatile dry obtains blocks of solid;
E) blocks of solid is placed in NH
3800-1000 ℃ of reduction in atmosphere;
F) product with step e mixes with binding agent, is expressed to carbon online.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000971B (en) * | 2011-09-15 | 2015-08-12 | 北汽福田汽车股份有限公司 | Lithium-air battery and preparation method thereof |
| CN102332568A (en) * | 2011-09-26 | 2012-01-25 | 复旦大学 | Cobalt oxide-diamond-like double-layer structured lithium-air battery cathode material and preparation method thereof |
| CN103123998B (en) * | 2011-11-18 | 2015-07-08 | 北汽福田汽车股份有限公司 | Preparation method for water-based lithium-air battery |
| CN103123961B (en) * | 2011-11-18 | 2015-07-08 | 北汽福田汽车股份有限公司 | Water-based lithium-air battery |
| CN102534630B (en) * | 2012-02-08 | 2014-01-01 | 武汉科技大学 | Porous titanium nitride nanotube array film and preparation method thereof |
| CN102593556B (en) * | 2012-03-07 | 2015-04-15 | 中国科学院宁波材料技术与工程研究所 | Lithium air or oxygen battery |
| CN102703953B (en) * | 2012-06-07 | 2014-11-26 | 北京工业大学 | Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition |
| CN103165905A (en) * | 2013-02-28 | 2013-06-19 | 北京化工大学常州先进材料研究院 | Air electrode of lithium-air battery and preparation method thereof |
| CN103151541A (en) * | 2013-03-01 | 2013-06-12 | 北京化工大学常州先进材料研究院 | Novel air electrode for lithium-air battery and preparation method |
| CN103952763B (en) * | 2014-05-15 | 2016-05-04 | 东南大学 | A kind of gold microsphere-titanium nitride nano pipe array composite material and its preparation method and application |
| CN108777294B (en) * | 2018-05-28 | 2020-12-25 | 福州大学 | Carbon-supported porous spherical MoN composed of nanosheets and application of carbon-supported porous spherical MoN as negative electrode material in lithium battery |
| CN109713250B (en) * | 2018-11-19 | 2021-05-25 | 北京泰丰先行新能源科技有限公司 | Preparation method of core-shell structure precursor of lithium battery positive electrode material |
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| CN101267057A (en) * | 2008-05-08 | 2008-09-17 | 复旦大学 | High ratio energy chargeable full-solid lithium air battery |
| CN101752627A (en) * | 2010-01-20 | 2010-06-23 | 中国科学院上海微系统与信息技术研究所 | High-energy-density metal lithium-air battery and production method thereof |
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| CN101165964A (en) * | 2007-09-20 | 2008-04-23 | 复旦大学 | Asymmetric secondary air fuel battery |
| CN101267057A (en) * | 2008-05-08 | 2008-09-17 | 复旦大学 | High ratio energy chargeable full-solid lithium air battery |
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